GB2073902A - Photographic light-sensitive material having subbed plastics support - Google Patents

Description

1

GB2 073 902A

1

SPECIFICATION

Photographic light-sensitive material having subbed plastics support

5 The present invention relates to photographic light-sensitive material and more particularly, to a 5 material in which the photographic layers are comprised of hydrophilic organic colloids coated on a plastic film support having a hydrophobic surface.

Films of polymers such as polyethylene terephthalate, cellulose triacetate, polystyrene or polycarbonate are now generally used as photographic materials, due to their desirable 10 characteristics such as a high degree of transparency and flexibility. However, difficulties arise 10 when using these polymers as support materials, for such supports have hydrophobic surfaces and photographic layers to be coated on the supports (e.g., a light-sensitive silver halide emulsion layer, an interlayer or a filter layer) have hydrophilic colloids such as gelatin as main component. Therefore, it is difficult to firmly adhere a photographic layer to the surface of the 15 support. In an attempt to obtain stronger adhesion, various treatments have been developed for 15 activating (rendering hydrophilic) the surfaces of hydrophobic supports.

Examples of types of surface activating treatments include chemical treatments, mechanical treatments, corona discharge treatments, flame treatments, ultraviolet ray treatments, high frequency wave treatments, flow discharge treatments, activated plasma treatments, laser 20 treatments, mixed acid treatments and ozone oxidation treatments. Two general techniques have 20 been used to increase adhesiveness between a hydrophobic support and a photographic layer. According to one technique, a photographic emulsion is coated directly on the surface of a hydrophobic support treated by one or more of the above-described surface treatments.

According to another technique, after a hydrophobic support has been treated by one or more of 25 the above-described surface treatments, a subbing layer is provided on the support and then a 25 photographic emulsion is coated on the subbing layer. This technique is described in U.S.

Patents 2,698,241, 2,764,520, 2,864,755, 3,462,335 and 3,475,193, British Patents 788,365, 804,005 and 891,469.

Of the two techniques, the latter is more effective and prevails now. All of the surface 30 treatments are intended to create polar groups to some degree. Some treatments also increase 30 cross-linking density at the surface of a support which is hydrophobic by nature. This increases the affinity for polar groups of a certain component contained in a subbing solution, as well as increasing the fastness at the interface formed between the support and the subbing layer by adhesion. In addition, various different subbing layers have been developed. For instance, to 35 make a double subbing layer, a support is coated first with a first subbing layer which adheres 35 well to the support and this first layer is coated then with a second subbing layer of a hydrophilic resin layer which can strongly adhere to a photographic layer. In a single layer process a resin having both hydrophobic and hydrophilic groups is coated on a support.

Both processes have been closely studied. A number of resins have been examined to 40 determine their usefulness as the first subbing layer in a double layer, for example, copolymers 40 have been prepared using as starting materials monomers selected from vinyl chloride,

vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid and maleic anhydride; polyethylene imine; epoxy resin; grafted gelatin; and nitrocellulose. Gelatins have been principally tested for their usefulness as a second subbing layer. These double layers have been 45 shown to possess satisfactory adhesion power to a conventional gelatin silver halide photo- 45

graphic emulsion. However, recently there has been a tendency to decrease the silver contents in silver halide photographic light-sensitive materials in order to conserve silver. In order to prevent the lowering in image density with a low silver content, it is necessary to extensively swell the photographic layers during development-processing. This requires a reduction in the 50 contents of hardeners in the photographic layers. When the hardener content is decreased, a 50 new problem develops involving the adhesion strength between a photographic layer and the second subbing layer; the adhesion becomes insufficient, particularly at the development-processing stage. Compositions used to make the first subbing layer may contain a large amount of a hardener, e.g. of the aldehyde series, active vinyl series or active halogen series; this 55 creates strong adhesion between the first subbing layer and the plastic film support. However, 55 the increased hardener content in the first subbing layer causes a reduction in adhesion strength between the second subbing layer and photographic layer. In addition, the subbing layer containing a large amount of hardener exerts undesirable influences upon photographic characteristics of the material, such as lowering the image density.

60 An object of the present invention is to provide a photographic light-sensitive material having 60 a double subbing layer and having strong adhesiveness between the second subbing layer and photographic layer, even when the hardener content in the photographic layer is reduced and/or a large amount of hardener is incorporated in the first subbing layer.

Another object is to provide such a material which can be prepared by use of a subbing 65 solution which has little adverse effects upon the photographic characteristics and which does 65

2

GB2073902A 2

not irritate human skin.

We have now found new types of second subbing layer which are effective for these purposes.

According to the present invention, a photographic light-sensitive material has, on a plastics 5 film support having a hydrophobic surface, two subbing layers and at least one photographic 5 lay^r containing a hydrophilic colloid binder coated on the second subbing layer; that photographic layer or another layer thereabove is a light-sensitive silver halide emulsion layer;

and the second subbing layer contains

(i) 0.01 to 2.0 grams, per square metre of the support, of a gelatin derivative, i.e. a

10 chemically modified gelatin as defined below, and/or 10

(ii) a polymer which contains at least 0.1 mol % of a recurring unit shown by the following general formula (I) or (II):

r

15t 15

-4ch2-c)—

(S02M)n (I)

20 20

wherein R represents a hydrogen or halogen atom or an alkyl group having 1 to 6 carbon 25 atoms; M represents a hydrogen, alkali metal or alkaline earth metal atom or an organic base; X 25 represents an alkyl, alkoxy or alkylamino group having 1 to 6 carbon atoms or a halogen atom; m is 0, 1 or 2; and n is 1 or 2,

30

CX,)m' CII)

35

wherein R' represents a hydrogen atom or an alkyl group; X' represents a hydrogen or halogen 40 atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, 40 an alkylsulfonyl group, an aryloxy group, a acyl group, an acyloxy group, or an acylamido group; m1 is 0, 1 or 2; and ri is 1 or 2.

In the first embodiment of the present invention, the essential component of the second subbing layer is a gelatin derivative. The term "gelatin derivative" as used herein means a 45 chemically modified gelatin formed as a result of a reaction of amino groups, imino groups, 45 carboxyl groups and/or hydroxyl groups of various amino acids making up the gelatin molecule with a mono-functional compound having a functional group as defined hereinafter.

The term "gelatin" is used to describe starting materials used for the preparation of the gelatin derivatives. Gelatin is a technical name for the protein substances derived from collagen. 50 The term gelatin herein includes any other synthetic products substantially equivalent to the 50 protein substances derived from collagen. The term "gelatin" includes: (1) alkali-processed gelatin obtained by processing collagen with lime or its equivalent; (2) acid-processed gelatin which involves processing collagen (or hide) with hydrochloric acid or its equivalent; (3) enzyme-processed gelatin which involves processing with hydrolase or its equivalent: and (4) low 55 molecular weight products obtained by subjecting each of these gelatins to hydrolytic cleavages 55 by various means. Any of the above-described gelatins can be used to prepare gelatin derivatives for the practice of the present invention.

A mono-functional compound which includes a functional group capable of undergoing a reaction with an amino, an imino, a carboxyl and/or a hydroxyl group (which groups are 60 contained in a gelatin molecule) is used in the preparation of gelatin derivatives. Typical 60

examples of functional groups as described above include -NCO, -NCS, -NH.C0.S03M -NH.CS.SO3M1 (wherein M1 represents an alkali metal such as sodium or potassium).

3

GB2 073 902A

3

5

CH-R1

/

-N R1 R2

\ I I

CH-R2, -NH-CH-CH-X1

(wherein R1 and R2 each is hydrogen or an alkyl group such as methyl, ethyl, propyl, butyl or isobutyl; and X1 is a halogen such as chlorine, bromine or fluorine), 10 10

R1 R1

I I

-a-c = ch2, -a-ch-ch2-b

15 (wherein R1 is defined above; a is an electron-attracting group which can activate the terminal 15 ethylenic bond, such as cyano, phenylsulfonyl, sulfamoyl, carbamoyl, sulfonyl or carbonyl group; and b is an atom or atoms capable of producing an ethylenic bonding at the terminal part by splitting an acid off the above-described functional group. The acid is formed by making b enter into combination with a hydrogen atom attached to the adjacent carbon. For example, b 20 can be a halogen atom such as bromine or chlorine, an acetyl group or sulfonic acid ester 20

residue). Other typical functional groups include -S02X' (wherein X' is defined above), -COX1 (wherein X1 is defined above),

25 , -ch-ch-r1 25

"< \/

^0 0

30 (wherein R1 is defined above), 30

OH

i

-ch- ..

35 35

(wherein X1 is defined above), -CH2X1 (wherein X1 is defined above), -COOR3 (wherein R3 is an aryl group having an electron attracting group at the ortho or the para position, such aso-nitrophenyl, p-nitrophenyl or />carboxylphenyl), and

40 o 40

» 1

/C-C-R

-N ||

c-ch

D

45 0 45

(wherein R1 is defined above).

Specific examples of the above-described mono-functional compounds suitable for the preparation of gelatin derivatives for the present invention are described below. They include 50 ("List a") isocyanates or the precursors thereof, such as phenyl isocyanate, p-tolyl isocyanate, 4- 50 bromophenyl isocyanate, 2-nitrophenyl isocyanate, 4-ethoxycarbonylphenyl isocyanate, 1-na-phthyl isocyanate, phenyl isocyanate-bisulfite adduct, 4-biphenyl isocyanate ■ bisulfite adduct; thioisocyanates or the precursors thereof, such as phenyl thioisocyanate, p-tolyl thioisocyanate,

phenyl thioisocyanate bisulfite adduct; aziridines or the precursors thereof, such as N-pentanoyl-55 2-ethyl-1-aziridine, 1-phenylcarbamoylaziridine, 2-methyl-1-phenylcarbamoylaziridine, 1-dimethy- 55 laminosulfonyl-aziridine, 1-benzoylaziridine, 4-nitrobenzoyl-1-aziridine, 1-(2-chlorophenyl)carba-moyl-1 -aziridine, 1 -(3-methylphenyl)carbamoylaziridine, 1 -(n-butylsulfonyl)aziridine, 1 -(phenylsul-fonyl)-2-methylaziridine, 2-(1-aziridinyl)-4,6-/b/s(ethylamino)-1,3,5-triazine, 1-phenyl-3-(2-choroe-thyl)urea; active vinyl compounds or the precursors thereof, such as N-vinylsulfonyl-p-toluidine, 60 vinylsulfonylbenzene, 1-methyl-4-vinylsulfonylbenzene, acrylonitrile, 1-(hydroxysulfonyloxy)-2-(4- 60 methoxyphenylsulfonyl)ethane, 2-phenylcarbamoylethyl bromide; sulfonyl halides such as ben-zenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride, 2-phenoxybenzenesulfonyl chloride; 4-chlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride, 3-nitrobenzenesulfonyl chloride, 3-carboxybenzenesulfonyl chloride, 2-naphthalenesul-65 fonyl chloride, 4-aminobenzenesulfonyl fluoride, 3,4-diaminobenzenesulfonyl fluoride, 3-carboxy- 65

4

GB2 073 902A

4

benzenesulfonyl fluoride; carboxylic acid halides such as 4-nitrobenzoyl chloride, 4-carboxyben-zoyl bromide; acid anhydrides such as succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, isatoic anhydride, monomethylsuccinic anhydride, glutaric anhydride, benzoic anhydride, trimellitic anhydride, 3,6-dichlorophthalic anhydride, diglycollic anhydride, nitrophthalic 5 anhydride; oxirane ring-containing compounds of the precursors thereof, such as 3-phenoxy-1,2- 5 epo.typropane, 3-(3-methylphenoxy)-1,2-epoxypropane, 3-(2,4- dibromophenoxy)-1,2-epoxypro-pane, 3-(4-acetylaminophenoxy)-1,2-epoxypropane, 3-(2-biphenyloxy)-1,2-epoxypropane, 3-(2,4-dinitro-1 -naphthoxy)-1,2-epoxypropane, 1 -chloro-2-hydroxy-3-phenoxypropane, epichlorohydrin, 1-bromo-2-hydroxy-3-(2-chlorophenyl)propane; halomethyl compounds such as bromoacetic 10 acid, chloroacetic acid; active esters such as o-nitropheny! benzoate, p-nitrophenyl acetate, p- 10 nitrophenyl-1-hydroxynaphthoate; and maleic acid imides such as N-ethyJmaleimide, N-phenyl-maleimide, N-(p-carboxyphenyl)-maleimide, N-(p-sulfophenyl)maleimide.

These compounds chemically modify gelatins in processes described below. The gelatin derivatives obtained as a result of the chemical modification greatly effect the adhesion of the *

1 5 second subbing layer to the hydrophilic organic colloid photographic layer coated upon the 1 5

second subbing layer. Compounds which can increase the number of carboxyl groups in the side-chain of the gelatin, such as succinic acid anhydride, phthalic acid anhydride or trimellitic acid anhydride, are preferable.

The gelatin derivatives are prepared by a general process in which gelatin is allowed to react 20 with one of the above-described mono-functional compounds. The reaction occurs in a solvent in 20 which the gelatin is soluble. Examples of useful solvents include water, an organic solvent such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, tretramethyl urea, tet-ramethylene sulfone, acetic acid, and a mixture of the organic solvent and water. The reaction proceeds in the presence of a base or acid which functions as a pH controlling agent.

25 In the gelatin derivative, at least one of the aforesaid fuctional groups (amino, imino, carboxyl 25 or hydroxy groups, preferably amino) in the gelatin molecule is chemically modified. The degree of substitution of any particular functional group in the chemical modification is preferably 50% or more. The substitution rate of an amino group is preferably 70% or more and more particularly 90% or more.

30 The gelatin derivative is preferably coated on the support in the second subbing layer in an 30 amount of 0.01 to 2.00 g (solid component), more particularly 0.05 to 0.50 g, per square meter of support, and should comprise at least 60 weight% of the layer.

In the second embodiment of the present invention, a polymer having the recurring unit of general formula (I) or (II) is used. A polymer of formula (I) includes a homopolymer obtained by 35 polymerizing the monomer shown by the following general formula (III), a copolymer obtained 35 by polymerizing the monomer of general fomula (III) with other monomers having at least one polymerizable unsaturated bond and a polymer obtained by introducing a sulfinic acid group into the side chain after finishing the aforesaid polymerization, as well as the derivatives of those polymers:

40

(S02M)n (III) 45

50 wherein the symbols are as defined above for formula (I); examples of R are a methyl or ethyl 50 group or a chlorine or bromine atom; examples of M are a sodium, potassium, calcium or magnesium atom or (an organic base) trimethylamine or triethylamine; and examples of X are chlorine and bromine.

In preferred polymers of formula (I) R is hydrogen, M is sodium or potassium, m is 0 and n is 55 1. 55

In preferred polymers of formula (II), R' is hydrogen, m' is 0 and n' is 1.

Specific examples of the monomer shown by general formula (III) are as follows:

5

GB2 073 902A 5

Monomer (A)

ch2=ch so2m

10

Monomer fBI

10

ch2»ch

15

Br

15

so2M

20 Monomer fC)

ch2=c(ch3)

25

s02m

20

25

30 Monomer fD)

ch2=ccj!,

35

S02M

and

30

35

40

40

Monomer CE)

45

50

ch2=ch so2m so2m

45

50

Among these monomers, a particularly preferred monomer is Monomer (A). Monomer (A) can 55 be prepared according to the process described in Chemistry Letters, 419-420 (1976) although 55 other process may be employed. Other monomers may be fundamentally prepared, if the corresponding sulfonic acid chloride is prepared, by the same process as described in the Chemistry Letters indicated above or by reducing the sulfonic acid chloride with a reducing agent such as sodium sulfite and, if desired, vinylating the product.

60 Also, the polymer having the recurring unit of general formula (I) may be prepared by the 60 above-described process using a polymer reaction wherein a polymer such as polystyrene is used as the starting material.

In general, any monomer having at least one polymerizable unsaturated bond may be used to copolymerize the monomer of formula (III). Examples of such polymerizable unsaturated 65 compound are allyl compounds such as allyl esters (e.g., allyl acetate, aliyl caproate, allyl 65

6

GB2073902A 6

caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lacetate), allyloxy ethanol, allyl butyl ether, allyl glycidyl ether, allyl phenyl ether; vinyl ethers (e.g., methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinvyl ether, methoxyethyl vinvyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl 5 ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl ether, hydroxyethyl vinyl ether, 5

diethyleneglycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butyraminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether,

vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether,

vinyl anthranyl ether); vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 10 isobutyrate, vinyldimethyl propionate, vinyl butyrate, vinyl valerate, vinyl caprate, vinylchloroa- 10 cetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenyl acetate,

vinyl acetoacetate, vinyl lactate, vinyl-/?-phenyl butyrate, vinylcyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate);

vinyl heterocyclic compounds such as N-vinyloxazolidone, N-vinylimidazole, N-vinylpyrrolidone, 15 N-vinylcarbazole, vinylthiophene, N-vinylethylacetamide; styrenes (e.g., styrene, methylstyrene, 15 dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluorome- . thylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methyl-styrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, 20 pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 20 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, vinylbenzoic acid methyl ester); crotonic acids such as crotonic acid, crotonic acid amide, crotonic acid ester (e.g., butyl crotonate, hexyl crotonate, glycerol monocrotonate); vinylketones (e.g., methyl vinyl ketone,

phenyl vinyl ketone, methoxyethyl vinyl ketone, olefins (e.g., dicyclopentadiene, ethylene); 25 propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 25 5-methyl-1-nonene, 5,5-dimethyl-1-octene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 5-me-thyl-1-hexene, 4-methyl-1-heptene, 5-methyl-1-heptene, 4,4-dimethyl-1-hexene, 5,6,6-trimethyl-1-heptene, 1-dodecene, 1 -octadecene, etc.); itaconic acids (e.g., itaconic acid, itaconic anhydride, methyl itaconate, ethyl itaconate); sorbic acid, cinnamic acid, methyl sorbate, glycidyl 30 sorbate, citraconic acid, chloroacrylic acid, mesaconic acid, maleic acid, fumaric acid, ethacrylic 30 acid, halogenated olefins (e.g., vinyl chloride, vinylidene chloride, isoprene), unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile), acrylic acids (e.g., acrylic acid, methyl acrylate), metha-crylic acids (e.g., methacrylic acid methyl methacrylate), acrylamides and methacrylamides.

Among these polymerizable unsaturated compounds, styrenes, vinyl heterocyclic compounds, 35 vinyl ethers, vinyl esters and defines are particularly preferred. 35

Examples of the polymer having the recurring unit shown by general formula (I) used in this invention are shown below, wherein the component ratios are all by mol ratio.

7

GB2 073 902A 7

CD

-{CH, -CH}—

i i x

S02Na

10 X21 10

-€ch2-CH^

15

so2K

25

S02Na x/y = 80/20

30 C41

-£CH2_P%-£CH2"CH^

35

Q Cf

S02Na

S02Na

60 x/y = 50/50

15

20 — 20

^CH^CH)^—6CH2-CH}-

y

'Nv^O

25

30

35

40

x/y = 50/50

40

(5)

^CH2-CH^-{CH2-CH^

45 r" n och3 45

S02Na

5Q x/y = 50/50 50

C6)

CH2-Ch^= fCH CHJ— 55

55 X I I 7 DO

<^•>1 o=c c=o I I

ONa ONa

60

8

GB2 073 902A

8

ia

5 ' 1 fa

S02Na S03K

x/y = 75/25

10 10

111

■fCH2-CH3Y-€CH2-CHJy

15 15

SOzNa

20 x/y = 70/30 20

C9)

2g -f CH2 -CH^Y-fCH, -CH^-^CH2 -CH=CH-CH2rz 25

SO-Na

30 2 30

x/y/z = 50/20/30

S02Na

S02Na

35

CiQ)

35 ^cH2-CH^r^CH2-CH^r

0

1

CH3

40 S0.,Na 40

x/y = 60/40

45 Xill 45

-{CHjj-CH^CHj-CHJy

OCCH-II 3

50 Y ° 50 ,

x/y - 80/20

55 55

C12)

-fCH2-CHJ—-6CH2-CH^-2 r X 2 , y

K 1 0H

60 k 'J 60

x/y = 80/20

9

GB2 073 902A 9

(13)

-fCH2-CH3Y-tCH2-CH>-

S02Na x/y = 5/9S

10 10

liil

15

-fCH^CH^CH^CH)-

' LZ 15

0CCH3

S02Na

20 x/y = 10/90 20

Examples of the polymer having the recurring unit shown by general formula (II) used in this 25 invention are shown below, wherein the component ratios are all by mole ratio.

25

C15)

30

35

-fCH^CH^

OH

30

35

(16)

40

45

-fCH2-CHJ-x

Br

OH

40

45

(17)

-£CH2"CH?-x

50

a

OH

50

55

60

65

(18)

-fCH2-CH>T-CCH2-CHV

OH 0-CH,C2.

II 2 o-

55

60

65

x/y = 60/40

10

GB2073902A 10

(19)

4CH2-CB}_eCH2-CH}-y oh ch2c*

10 x/y" 75/25 10

(20)

-ech,-ch3—-fch ,-chfc- i

15 lKY ™S 15

-c-cch2)3-c(ch3)3 C2«S

20 x/y = 75/2S 20

c2hs

OH L b

(21)

25 -eCH2-CH^r6CH2-CH3^ 25

C=0

I

oc4h9

30 °H 30

x/y = 45/SS

(22)

35 35

-6ch2 - ch^-tch2 - ch= ch - ch2^-6ch2 - ch^

cooh

40 oh 40

x/y/z = 5S/40/S

11

GB2 073 902A

1231

-{ch2-ch}^—£ch—ch)-

0=c c=0

I I

oh oc4h9

oh

10

x/y = 50/50

10

(24)

15

20

ch,

-iCH2-C^

oh

15

20

1251

25 -fCH2-CH>r-fCH2-CHV

30

oh o-ch2-ch-ch2ca

25

30

oh x/y = 20/80

35

35

Of these polymers, compounds (1), (2) and (15) are more preferred, and compound (15) is most preferred.

40 Compounds (1 5) to (25) may be prepared in known manners, for example, by the 40

polymerization processes described in Journal of Polymer Science, A-1, Vol. 7, pp. 2175 and 2405 using the monomers prepared by the processes described in Journal of Organic Chemistry, Vol. 23, p. 544 (1958). Furthermore, some of the above-described compounds can be used in the form of commercially available products; for example, the polymer shown as 45 Compound (15) is available under the trade name "Resin M", and Compound (16) is available 45 under the trade name "Resin MB" marketed by Maruzen Oil Co., Ltd.

It is necessary that the polymer having the recurring unit shown by general formula (I) or (II)

used in this invention contains at least 0.1 mole % preferably 1 mol % or more, more preferably 10 mol % or more, of the recurring unit of general formula (I) or (II). When one or ' 50 more of these polymers is present in the second subbing layer in an amount of 0.01 to 99% by 50 weight, preferably 0.1 to 50% by weight, more particularly 1 to 20% by weight, based on the solid content of a binder in the second subbing layer, the desired effect is obtained.

The second subbing layer preferably contains a binder in addition to the above-described polymer or polymers. Examples of the binder are hydrophilic colloids such as proteins (e.g., 55 gelatin, colloidal albumin, casein), cellulose compounds (e.g., carboxymethyl cellulose, hydroxy- 55 ethyl cellulose), sugar derivatives (e.g., agar agar, sodium alginate, starch derivatives), and synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamide, and the derivatives and partially hydrolyzed products thereof.

If desired, two or more kinds of these colloids may be used. Among them, however, gelatin is 60 more generally used. Gelatin includes so-called lime-processed gelatin, acid-processed gelatin 60 and enzyme-processed gelatin.

Various additives may be included in the subbing solution for the second subbing layer.

Examples of such additives include: a matting agent, a surface active agent, an antistatic agent, an intihalation agent, a coloring dye, pigments, a coating aid and an antifogging agent. The 65 matting agent is an inorganic or an organic fine powder which has an average grain size of 1 to 65

12

GB2 073 902A

12

5 microns. Examples of an inorganic matting agent include silica (silicon dioxide), magnesium oxide, titanium dioxide and calcium carbonate. Examples of an organic matting agent include polymethylmethacrylate, cellulose acetate propionate and polystyrene. Of these matting agents preferably ones are silica and polymethylmethacrylate, especially polymethylmethacrylate.

5 The first subbing layer may contain various macromolecular substances to increase adhesion 5 to the plastic film support. Examples of macromolecular substances in the first subbing layer include copolymers which are prepared from vinyl chloride, vinylidene chloride, methacrylic acid, acrylic acid, methacrylic acid ester, acrylic acid ester, itaconic acid, maleic anhydride, vinyl acetate, butadiene or styrene. The copolymers which use as one of starting materials butadiene, 10 styrene or vinylidene chloride are preferred. Synthesis examples and usage examples of these 10 copolymers are described in detail in Japanese Patent Publications 13092/60 and 11779/61, Japanese Patent Applications (OPI) (the term "OPI" as used herein refers to a "published unexamined Japanese patent application") 43911/75, 13151 6/75, 1 35971 /76, 49019/77, 58469/76, 117617/76, 121323/76, 123139/76, 139320/76, 65422/77, 96016/77, -15 108114/77, 109923/77, and 114121/76, U.S. Patents 3,645,740, 4,087,574 and 15

4,039,333, and British Patents 1,271,921, 1,532,517 and 1,520,076.

It is desirable to use a hardening agent in the first subbing layer. Examples of the hardening *

agent include: aldehyde series compounds such as formaldehyde, glyoxazole; ethyleneimino group-containing compounds such as mucochloric acid, tetramethylene-1,4-bis(ethyleneurea), 20 hexamethylene-1,4-bis(ethyleneurea); methane sulfonates such as trimethylenebismethanesulfon- 20 ate; active vinyl compounds such as bisacryloyl urea, n>xylenedivinyl sulfone; active halogen-containing compounds such as 2-methoxy-4,6-dichlorotriazine; epoxy group-containing compounds such as bisphenol glycidyl ether; and isocyanates. Of these hardening agents, active halogen compounds, expecially 2,4-dichloro-6-hydroxy-s-triazine sodium salt are particularly 25 effective. 25

The subbing solution for the first subbing layer may include various additives. Examples of these additives include surface active agents, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids and anti-foggants. The subbing solution used for making the first subbing layer does not require any etching agent, such as resorcinol, chloral hydrate or 30 chlorophenol. However, an etching agent may be contained in the first subbing layer. 30

When a conventional subbing layer is placed on a plastic film support and a photographic layer containing a reduced amount of a hardener (to control photographic characteristics) is coated thereon, insufficient adhesion is obtained between the subbing layer and the photographic layer. However, when a gelatin derivative as described above or polymers having the 35 repeating units of general formula (1) and/or the repeating unit of general formula (II) is 35

incorporated in the subbing layer, strong adhesive power is unexpectedly obtained between the second subbing layer and a photographic layer. The improved adhesiveness is obtained even when the amount of the hardener in the photographic layer is reduced. Further, if a polymer having the repeating unit of general formula (I) and/or the repeating unit of general formula (II) 40 is incorporated in the second subbing layer in addition to the gelatin derivatives, the 40

adhesiveness between the second subbing layer and the photographic layer can be further strengthened.

The present subbing solutions can be coated using general well-known coating techniques.

Examples of useable methods include: dip coating, air knife coating, curtain coating, roller 45 coating, wire bar coating, gravure coating and extrusion coating utilizing a hopper as described 45 in U.S. Patent 2,681,294. Further, a plurality of layer can be coated at the same time using techniques as described in U.S. Patents 2,761,791, 3,508,947, 2,941,898 and 3,526,528, ? and Yuji Harazaki, Kotingu Kogaku (Coating Engineering), p. 253, Asakura Shoten, Tokyo (1 973). The subbing layer may be comprises of first and second subbing layers, and either of 50 the two subbing layers may be comprises of a plurality of layers. 50 -

After the subbing layers have been coated on the support, they are dried in a subsequent drying process. Drying may be carried out at a temperature of 120°C to 200°C for 30 seconds to 10 minutes. The optimum drying conditions can be determined within the above-described ranges for each specific case.

55 The thickness of the second subbing layer used according to the present invention is not 55

limited to any particular range. However, the thickness of the second subbing layer is preferably 0.01 to 1.0 micron.

The term "plastic film support" is intended to include films made oft plastics, such as cellulose esters (especially cellulose triacetate, cellulose diacetate and cellulose propionate), polyamides, 60 polycarbonate, polyesters (especially polyethylene terephthalate, poly-1,4-cyclohexanedimethy- 60 lene terephthalate, and polyethylene 1,2-diphenoxyethane-4,4'-dicarboxylate), polystyrene, polypropylene, polyethylene, and complex films made by coating or laminating the above-described plastics or plastic films, respectively, on papers or other supports.

Among these films, polyethylene terephthalate films are the best. In particular, polyethylene 65 terephthalate films drawn in the biaxial directions and fixed thermally are desirable due to their 65

13

GB2 073 902A

13

excellent stability, sturdiness.

The thickness of the plastic film support is not limited to any particular range. However, films having a thickness of 1 5 ju to 500 /z, especially 40 n to 200 ju., have desirable handling properties and wide applicability.

5 The support may be transparent, or contain dyes, or pigments, such as titanium dioxide. In 5 addition, the support may contain silicon dioxide, alumina sol, chromium salts or zirconium salts.

A photographic light-sensitive material is made by coating photographic layers on a support which has provided thereon subbing layers in accordance with the present invention. The 10 coating is carried out using a commonly known coating technique. 10

The photographic layers include silver halide photographic emulsion layer, an interlayer, a filter layer, a surface protecting layer and a backing layer.

The photographic layers each contains a hydrophilic colloid as a binder. Examples of the hydrophilic colloid include: gelatin, phthalated gelatin, maleated gelatin, carboxymethyl cellu-15 lose, hydroxyethyl cellulose, grafted gelatin, polyvinyl alcohol, polyhydroxyalkylacrylate, polyvi- 15 nyl pyrrolidone and vinyl pyrrolidone-vinyl acetate copolymers. In addition to the hydrophilic colloids, the photographic layers may contain dispersions of synthetic polymers insoluble or slightly soluble in water. Useful synthetic polymers include: homopolymers prepared using as a monomer component such as an alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate, glycidyl(meth)a-20 crylate, (meth)acryl amide, vinyl ester (e.g., vinyl acetate), acrylonitrile, olefin or styrene; and 20 copolymers prepared using a combination of a plurality of monomer components selected from the above described monomers. Other usefull copolymers include those prepared using as monomer components a combination of one or more monomer selected from the above-described one with one or more monomers selected from acrylic acid, methacrylic acid, a,/3-25 unsaturated dicarboxylic acid, hydroxyalkyl(meth)acrylate, sulfoalkyl(meth)acrylate and styrene 25 sulfonic acid. These polymers are described in U.S. Patents 2,376,005, 2,739,137,

2,853,457, 3,062,674, 3,411,911, 3,488,708, 3,525,620, 3,607,290, 3,635,715 and 3,645,740, and British Patents 1,186,699 and 1,307,373.

The photographic layer may also contain silver halide grains, chemical sensitizers, an anti-30 foggant, a stabilizer, a hardener, an antistatic agent, a coating aid, a matting agent, a 30

brightening agent, spectral sensitizing dyes, dyes and color couplers. Additives such as these are disclosed within Research Disclosure, Vol. 176, pp. 22-31 (December, 1978).

The present invention will now be illustrated in greater detail by reference to the following examples. However, the invention is not intended to be construed as being limited to these 35 examples. 35

Syntheses of the gelatin derivatives may carried out using a method as described in U.S.

Patent 3,923,51 7.

The adhesion test in each of the following examples was carried out in the following manner:

40 (1) Adhesion test in a dried condition: 40

The emulsion sides of a raw stock film and a film which was developed and dried are cut reticulately at about 4 mm intervals with a blade of a razor. To the resulting emulsion surface, adhesive tape (made by Sumitomo 3M Co., Ltd., having the registered trade name of Scotch Permacell Tape) is applied. The tape is then peeled off quickly. When the emulsion layer is 45 peeled off together with the adhesive tape in a proportion of not more than 5%, the film is 45

ranked grade A. When the peeled-off proportion is from 5% to not more than 30%, the film is graded B, and when it is 30 to 100%, the film is graded C.

(2) Adhesion test in a wet condition:

50 At each of the stages of development, fixing and washing, two crossed scratches are inflicted 50 on the emulsion side of a film with a stencil pen in the processing solution. The resulting scratched part is rubbed with a finger tip in the direction perpendicular to each of scratch lines.

When the emulsion layer peels off in the scratched part alone, the film is ranked grade A. When the maximum width of the peeled-off part is narrower than 5 mm, the film is graded B, and 55 when it is not narrower than 5 mm, the film is graded C. 55

EXAMPLE 1

A first subbing layer having a composition described in Table 1 was provided on a biaxially oriented polyethylene terephthalate film. The coated film was dried at 180°C for 1 minute. A 60 second subbing layer having any of the compositions described in Table 1 was provided on the 60 first subbing layer, dried at 120°C for 1 minute and, thereafter, submitted to a heat treatment at 140°C for 5 minutes. Several kinds of silver iodobromide photographic emulsions (iodide content: 2.5 mol%) for radiographs which differed from one another in their hardener contents were prepared. The hardener contents are described in Table 1. On the subbing layer-coated 65 film base, each of these silver halide emulsions was coated at the coverage of 3 g silver and 3.5 65

14

GB2 073 902A

14

g gelatin per square meter. Thus, Samples (11) to (19) having compositions set forth in Table 1 were obtained.

TABLE 1

Composition of Each Sample

Sample No

(11) (12) (13)

(14)

First Subbing Layer

Butadiene-styrene-acrylic acid copolymer latex (solid content: 50%, polymerization ration by weight: 35/63/2: 10 cc

2,4-Dichloro-6-hydroxy-s-triazine-sodium salt (8% aqueous solution): 2 cc

Distilled water: 150 cc

Second Subbing Layer

Lime- Lime- Acid-processed processed processed gelatin gelatin gelatin 0.10 g/m2 0.10 g/m2 0.10 g/m2

Acid processed gelatin 0.10 g/m2

Dry Thickness

The first subbing layer: about 0.5 /x The second subbing layer: about 0.1 ju.

Hardener in Photographic Layer

2,4-Dichloro-6-hydroxy-s-triazine • sodium salt

2 mmol/ 1 mmol/ 2 mmol/ 100 g gelatin 100 g gelatin 100 g gelatin

1 mmol/ 100 g gelatin

TABLE 1 (cont'd)

Sample No.

(15) (16) (17) (18)

(19)

First

Subbing Layer

Butadiene-styrene-acrylic acid copolymer latex (solid content: 50%, polymerization ratio by weight: 35/63/2): 10 cc

2,4-Dichloro-6-hydroxy-s-triazine-sodium salt (8% aqueous solution): 2 cc Distilled Water: 150 cc

Second Subbing Layer

*1 *2 *3 *4 Phthalated Trimellitylated Succinylated Phenylcarbamylated gelatin gelatin gelatin gelatin 0.10 g/m2 0.10 g/m2 0.10 g/m2 0.10 g/m2

*5

Acetylated gelatin 0.10 g/m2

Dry Thickness

The first subbing layer: about 0.5 ju The second subbing layer: about 0.1 ju

Hardener in

Photographic

Layer

2,4-Dichloro-6-hydroxy-s-triazine-sodium salt: 1 mmol/100 g gelatin

*1 to *5: Substitution rate for amino group is 90% in each case.

17

GB2 073 902A

17

The adhesiveness of each sample in the dried condition and in the wetted condition are shown in Table 2.

TABLE 2 5 Result of Adhesion Test

Sample No.

(11) (12)

(13)

(14)

(15)

(16)

(17)

(18)

(19)

Dry

A A

A

A

A

A

A

A

A

Wet

B C

B

C

A

A

A

B

B

10 10

15 The results in Table 2 show the adhesiveness decreases as the hardener content in the 15

photographic layer is decreased. Table 2 shows that samples (15) to (19), in which gelatin derivatives were used, exhibited excellent adhesiveness even when the hardener contents in their photographic layers were reduced. Of these samples, those wherein the second subbing layer contained phthalated gelatin, trimellitylated gelatin or succinylated gelatin were found to 20 exhibit particularly excellent adhesiveness 20

EXAMPLE 2

A polyethylene terephthalate film is coated with the same first subbing layer as in Example 1. The first subbing layer is coated with a second subbing layer of phthalated gelatins, which differ 25 from one another in the substitution rate for the amino group as shown in Table 3. The coated 25 film was dried at 120°C for 1 minute and then subjected to a heat treatment at 140°C for 5 minutes. Next, a silver halide emulsion for a radiograph was coated in the same manner as in Example 1, and Samples (21) to (26) were obtained.

30 TABLE 3 30

Composition of Each Sample

Sample No.

35 (21) (22) (23) (24) (25) (26) 35

Second Subbing Layer Constituent

40 Substance Phthalated gelatin: 0.10 g/m2 40 Substitution

Rate 0% 30% 50% 70% 85% 95%

45 Dry Thickness First subbing layer: about 0.5 ju 45 Second subbing layer: about 0.1 /x

Hardener in 2,4-Dichloro-6-hydroxy-s-triazine-sodium

Photographic salt: 1 mmol/100 g gelatin

50 Layer 50

The samples exhibited adhesion powers as shown in Table 4 in the dried and the wetted conditions, respectively.

18 GB2 073 902A 18

TABLE 4

Result of Adhesion Test

5 Sample No. 5

(21) (22) (23) (24) (25) (26)

Dry A A A A A A 10 Wet C C C B A A 10

As can be seen from Table 4, the higher the substitution rate of the gelatin derivative contained in the second subbing layer, the greater the adhesiveness created. «

15 15

EXAMPLE 3

A polyethylene terephthalate film is coated with the same first subbing layer as Example 1. A «

second subbing layer having a composition as shown in Table 5 was coated on the first subbing layer, dried at 120°C for 1 minute and, thereafter, subjected to a heat treatment at 140°Cs for 20 five minutes. A silver halide emulsion for a radiograph is coated on the second subbing layer in 20 the same manner as in Example 1. Thus, Samples (31) to (37) were obtained.

TABLE 5

Composition of Each Sample

Sample No.

(31) (32)

(33)

(34)

(35)

(36)

(37)

Second

Subbing

Layer

Matting Agent

Dry Thickness

Hardener in

Photographic

Layer

Phthalated gelatin (Substitution rate: 70%): 0.10 g/m2

Polymer Compound No. (2)

Polymer Compound No. (15)

0.05 g/ 1 g gelatin

0.10 g/ 1 g gelatin

0.05 g/ 1 g gelatin

0.10 g/ 1 g gelatin

-(CH2-CH)-n COONa

0.05 g/ 1 g gelatin

Polymethylmethacrylate (average grain size of 2fim): 5 mg/m2

The first subbing layer: about 0.5 /x The second subbing layer: about 0.1 ju,

2,4-Dichloro-6-hydroxy-s-triazine-sodium salt: 1 mmol/100 g gelatin

0.10 g/ 1 g gelatin

20

GB2 073 902A

20

The adhesion powers exhibited by the samples in both dried and wetted conditions are shown in Table 6.

TABLE 6

5 Result of Adhesion Test 5

Sample No.

(31) (32) (33) (34) (35) (36) (37)

10 10

Dry A A A A A A A Wet B A A A A B B

15 Table 6 shows that the addition of the polymer represented by Compound No. (2) or (15) to the gelatin derivative contributed to increasing adhesiveness.

15

EXAMPLE 4

A polyethylene terephthalate film is coated with the same first subbing layer as Example 1. A 20 second subbing layer having a composition as set forth in Table 7 was coated on the first 20

subbing layer, dried at 120°C for 1 minute and, thereafter, subjected to a heat treatment at 140°C for 5 minutes. A silver halide emulsion for a radiograph was coated on the second subbing layer in the same manner as in Example 1. Thus, Samples (41) to (46) were prepared.

25 Table 7

Composition of Each Sample

Sample No.

30

(41) (42)

(43)

(44)

(45)

(46)

Second Subbing Layer

Phthalated gelatin*/Lime processed gelatin (weight ratio)

35

1/0 0.8/0.2 0.10 g/m2

0.6/0.4 0.4/0.6 0.2/0.8 0/1

40

Dry Thickness

45

Hardenerin

Photographic

Layer

The first subbing layer: about 0.5 /i The second subbing layer: About 0.1 n

2,4-Dichloro-6-hydroxy-s- triazine-sodium salt: 1 mmol/100 g gelatin

50

'Having subsitution rate of 90%

The adhesion powers exhibited by the samples in both dried and wetted conditions are set forth in Table 8.

TABLE 8

Result of Adhesion Test

55

60

Sample No.

(41)

(42)

(43,

(44)

(45)

(46)

Dry

A

A

A

A

A

A

Wet

A

A

B

C

C

C

25

30

35

40

45

50

55

60

Table 8 shows that the higher the content of phthalated gelatin in the second subbing layer, the greater the adhesive in the wet.

65 EXAMPLE 5

65

21

GB2 073 902A 21

A first subbing layer having a composition described in Table 9 was provided on a polyethylene terephthalate film. The film had been oriented and crystallized by receiving a drawing treatment in a biaxial direction. The coated film was dried at 120°C for 3 minutes. A second subbing layer having any of the compositions described in Table 9 was provided on the 5 first subbing layer, dried at 120°C for 1 minute and then subjected to a heat treatment at 5

140°C for 5 minutes. Silver halide emulsions for radiographs were prepared containing different amounts of hardener as shown in Table 9. These emulsions were coated on the second subbing layer in the same manner as in Example 1. Thus, samples (51) to (59) were obtained.

TABLE 9

Composition of Each Sample

Sample No.

(51)

(52)

(53)

(54)

First Subbing Layer

Second Subbing Layer

Dry Thickness

Hardener in Photographic Layer

The subbing solution 4 described in Example 3 of U.S. Patent 4,087,574.

Lime-processed gelatin 0.10 g/m2

Lime-processed gelatin 0.10 g/m2

Acid-processed gelatin 0.10 g/m2

The first subbing layer: about 0.5 n The second subbing layer: about 0.1 ju

2,4-Dichloro-6-hydroxy-s-triazine-sodium salt

2 mmol/ 1 00 g gelatin

1 mmol/ 100 g gelatin

2 mmol/ 100 g gelatin

Acid-processed gelatin 0.10 g/m2

1 mmol/ 100 g gelatin

TABLE 9 (cont'd)

Sample No.

(55) (56) (57)

(58)

(59)

First Subbing Layer

The subbing solution 4 described in Example 3 of U.S. Patent 4,087,574

Second Subbing Layer

»1 *2 *3 Phthalated Trimellitylated Succinylated gelatin gelatin gelatin 0.10 g/m2 0.10 g/m2 0.10 g/m2

*4

Phenylcarbamylated gelatin

0.10 g/m2

*5

Acetylated gelatin 0.10 g/m2

Dry Thickness

The first subbing layer: about 0.5 ju, The second subbing layer: about 0.1 ju,

Hardener in Photographic Layer

2,4-Dichloro-6-hydroxy-s-triazine-sodium salt: 1

mmol/100 g gelatin

*1 to *5: Substitution rate for amino group is 90% in each gelatin derivative.

24 GB2 073 902A 24

These adhesive powers exhibited by the samples in both dried and wetted conditions are shown in Table 10.

TABLE 10

5 Result of Adhesion Test 5

Sample No.

(51) (52)

(53)

(54)

(55)

(56)

(57)

(58)

(59)

Dry

A A

A

A

A

A

A

A

A

Wet

B C

B

C

A

A

A

B

B

15 Table 10 shows that samples (55) to (59) exhibited excellent adhesiveness even when the 15 hardener contents in their photographic layers were reduced. Of these samples, those containing phthalated gelatin, trimellitylated gelatin or succinylated gelatin were found to exhibit particularly excellent adhesiveness.

20 COMPARISON EXAMPLE 20

A first subbing layer having the composition shown in Table 1 1 was formed on a biaxially oriented polyethylene terephthalate film and dried for 1 minute at 180°C. Then, a second subbing layer having the composition shown in Table 11 was formed on the first subbing layer,

dried for 1 minute at 120°C, and heat-treated for 5 minutes at 140°C. On the subbing layer-25 coated film base was coated a radiographic silver halide emulsion (AgBrl, I = 2.5 mol%) with 3 25 g of silver and 3.5 g of gelatin per square meter. By changing the coverage of the hardening agent shown in Table 11, Samples (101) to (105) were obtained.

TABLE 11

Composition of Each Sample

Sample No.

(101) (102) (103) (104)

(105)

First Subbing Layer

Butadiene-styrene-acrylic acid copolymer latex (solid content: 50%, polymerization ratio by weight: 35/63/2): 10 cc

2,4-Dichloro-6-hydroxy-s-triazine • sodium salt (8% aqueous solution): 2 cc Distilled water: 1 50 cc

Second Subbing layer

Lime-processed gelatin: 0.10 g/m2

Dry Thickness

First subbing layer: about 0.5 ju Second subbing layer: about 0.1 ju

Hardener in Photographic Layer

2,4-Dichloro-6-hydroxy-s-triazine • sodium salt

0.5 mmol/ 1 mmol/ 2 mmol/ 3 mmol/ 100 g gelatin 100 g gelatin 100 g gelatin 100 g gelatin

4 mmol/ 100 g gelatin

26 GB2 073 902A 26

The adhesive strengths of the samples thus-obtained when dry and wet are as shown in Table 12.

TABLE 12 5 Result of Adhesion Test

Sample No.

(101) (102) (103) (104) (105)

10 10

Dry A A A A A

Wet C C C B A

15 From the results shown in Table 12, it is understood that the wet adhesive strength is 15

insufficient when the amount of the hardener in the photographic layer is reduced and the second subbing layer consists of an unmodified gelatin.

EXAMPLE 6

20 A first subbing layer having the composition of the Comparison Example was formed on a 20 polyethylene terephthalate film, and a second subbing layer having the composition as shown in Table 13 was formed thereon. The layers were dried for 1 minute at 120°C and then heat-treated for 5 minutes at 140°C. Then, a radiographic silver halide emulsion was coated thereon as in the Comparison Example while changing the amount of the hardener as shown in Table 13 25 to provide Samples (61) to (67). 25

TABLE 13

Composition of Each Sample

Sample No.

(61)* (62)

(63)

(64)

(65)

(66)

(67)

Second Sub

Lime-processed gelatin:

0.10 g/m2

bing Layer

Polymer of

Polymer of

Polymer of

Polymer of

Polymer of

Polymer of

— Compound

Compound

Compound

Compound

Compound

Compound

No.

No.

No.

No.

No.

No.

(1)

(1)

(1)

(15)

(15)

(15)

0.05 g/

0.10 g/

0.15 g/

0.05 g/

0.10 g/

0.15 g/

— g-gelatin g-gelatin g-gelatin g-gelatin g-gelatin g-gelatin

Dry Thick

First subbing layer: about 0.5 ft

ness

Second subbing layer: about 0.1 ju

Hardener in

2,4-Dichloro-6-hydroxy-s-triazine • sodium salt

Photographic

Layer

2 mmol/ 1 mmol/

1 mmol/

1 mmol/

1 mmol/

1 mmol/

1 mmol/

100 g- 100 g-

100 g-

100 g-

100 g-

100 g-

100 g-

gelatin gelatin gelatin gelatin gelatin gelatin gelatin

* Comparison Sample

28

1

GB2 073 902A 28

The adhesive strengths of the samples thus-obtained when dry and wet are as shown in Table 14.

TABLE 14 5 Result of Adhesion Test

Sample No.

(61)*

(62)

(63)

(64)

(65)

(66)

(67)

Dry

A

A

A

A

A

A

A

Wet

C

A

A

A

A

A

A

10 10

15* Comparison sample 1 5

From the results shown in Table 14, it is understood that Samples (62) to (67) containing Compound No. (1) or (15) show good adhesive strength as compared with Comparison Example " (61). The improved results are observed even when the amount of the hardener in the photographic layer is reduced to half the amount in the comparison sample. 20 20

EXAMPLE 7

A first subbing layer having the composition of the Comparison Example was formed on a polyethylene terephthalate film, and a second subbing layer as shown in Table 15 was formed thereon. The layers were dried for 1 minute at 120°C and then heat-treated for 5 minutes at 25 140°C. Thereafter, a radiographic silver halide photographic emulsion was coated thereon while 25 changing the amount of the hardener as shown in Table 1 5 to provide samples (71) to (78).

TABLE 15

Composition of Each Sample

Sample No.

(71)* (72)

(73)

(74)

(75)

(76)

(77)

(78)

Secon Sub

Lime-processed gelatin:

o o

CQ

NJ 1

i

bing Layer

Polymer

Polymer

Polymer

Polymer

Polymer

Polymer

-(CH2-

-CH)-n

of of of of of of

|

— Compound

Compound

Compound

Compound

Compound

Compound

C-ONa

No.

No.

No.

No.

No.

No.

||

(3)

(7)

(12)

(16)

(19)

(24)

0

— 0.10 g/g-

0.10 g/g-

0.10 g/g-

0.10 g/g-

0.10 g/g-

0.10 g/g-

0.10 g/g-

gelatin gelatin gelatin gelatin gelatin gelatin gelatin

Dry Thick

First Subbing layer: about 0.5 /i

ness

Second subbing layer: about 0.1 /n

Hardener in

2,4-Dichloro-6-hydroxy-s-triazine • sodium salt

Photographic

Layer

2 mmol/ 1 mmol/

1 mmol/

1 mmol/

1 mmol

1 mmol/

1 mmol/

1 mmol/

100 g- 100 g-

100 g-

100 g-

100 g-

100 g-

100 g-

100 g-

gelatin gelatin gelatin gelatin gelatin gelatin gelatin gelatin

* Comparison Sample

30

GB2 073 902A 30

The adhesive strengths of the samples thus-obtained at drying and wetting are as shown in Table 16.

TABLE 16 5 Result of Adhesion Test

Sample No.

(7ir (72) (73) (74) (75) (76) (77) (78)*

10

Dry A AAAAAAA Wet C A A A A A A C

* Comparison Sample

15

From the results shown in Table 16, it is understood that Samples (72) to (77) containing polymers of Compounds Nos. (3), (7), (12), (16), (19) and (24) used in this inventon in the second subbing layers have good adhesion even if the amount of the hardener in the photographic layer is reduced to half of the Comparison sample (71).

20

EXAMPLE 8

A first subbing layer having the composition shown in Table 1 7 was formed on a biaxially oriented polyethylene terephthalate film. The layer was dried for 3 minutes at 120°C. Then, on the first subbing layer was formed a second subbing layer having the composition shown in

25 Table 17. The layer was dried for 1 minute at 120°C and thereafter heat-treated for 5 mjnutes at 140°C. Then, a radiographic silver halide emulsion was coated thereon while changing the amount of the hardener as shown in Table 17 to provide Samples (81) to (87).

TABLE 1 7

Composition of Each Sample

Sample no.

(81)*

(82)

(83)

(84)

(85)

(86)

(87)

First Subbing Layer

Second Subbing Layer

Dry Thickness

Hardener in

Photographic

Layer

The subbing solution 4 described in Example 3 of U.S. Patent 4,087,574

Lime-processed gelatin: 0.10 g/m2

Polymer of Compound No.

(2)

0.05 g/ g-gelatin

Polymer of Compound No.

(2)

0.15 g/ g-gelatin

Polymer of Compound No.

(15)

0.05 g/ g-gelatin

First subbing layer: about 0.5 jJL Second subbing layer: about 0.1 /x

2,4-Dichloro-6-hydroxy-s-triazine-sodium salt

2 mmol/ 1 mmol/ 1 mmol/ 1 mmol/ 100 g- 100 g- 100 g- 100 g-

gelatin gelatin gelatin gelatin

Polymer of Compound No.

(15)

0.15 g/ g-gelatin

1 mmol/ 100 g-gelatin

-(CH2-CH)-

I

COONa

0.05 g/ g-gelatin

0.15 g/ g-gelatin

1 mmol/ 100 g-gelatin

1 mmol/ 100 g-gelatin

'Comparison Sample

32 GB2 073 902A 32

The adhesive strength of the sample thus-obtained at drying and wetting is as shown in Table 18.

TABLE 18 5 Results of Adhesion Test

Sample No.

10 (81)* (82) (83) (84) (85) (86) (87) 10

Dry A A A A A A A Wet C A A A A C C

15 * Comparison Sample 15

From the results shown in Table 18, it is understood that Samples (82) to (85) containing ?

Compound No. (2) or (1 5) have good adhesion as compared with that of Comparison Example (81). The improved adhesion is apparent even when the amount of the hardening agent is

20 reduced to half that of Comparison Example (81). 20

Claims (21)

1. A photographic light-sensitive material comprising a plastics film support having a hydrophobic surface on which surface are coated, in order,

25 a first subbing layer, 25

a second subbing layer, and a photographic layer containing a hydrophilic colloid, wherein the second subbing layer contains a gelatin derivative (as hereinbefore defined) in an amount of 0.01 to

2.0 grams per square metre.

30 2. A photographic material as claimed in Claim 1, wherein at least 50% of any functional 30 group contained in the gelatin used to produce said gelatin derivative has been chemically modified by substitution reaction.

3. A photographic material as claimed in Claim 2, wherein said modified functional group is an amino group.

35

4. A photographic material as claimed in Claim 1, 2 or 3, wherein said gelatin derivative 35 was prepared by chemically modifying a gelatin with an agent which was selected from any of those listed hereinbefore in List A.

5. A photographic material as claimed in Claim 4, wherein said agent increases the number of carboxylic groups in a side chain of said gelatin.

40

6. A photographic material as claimed in Claim 5, wherein said agent is an acid anhydride. 40

7. A photographic material as claimed in Claim 5, wherein said acid anhydride is succinic anhydride, phthalic anhydride or trimellitic anhydride.

8. A photographic material as claimed in any of Claims 1 to 7, wherein said gelatin derivative comprises at least 60 wt% of said second subbing layer.

45

9. A photographic light-sensitive material comprising a plastics film support having a 45

hydrophobic surface on which surface are coated, in order,

a first subbing layer,

a second subbing layer, and a photographic layer containing a hydrophilic colloid, wherein said second subbing layer

50 contains a polymer which contains at least 0.1 mol% of a recurring unit represented by the 50

following general formula (I) and/or (II):

(so2M)n (i)

55

60

65

wherein R represents a hydrogen or halogen atom or an alkyl group having 1 to 6 carbon atoms; M represents a hydrogen, alkali metal or alkaline earth metal atom or an organic base; X represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 65

33

GB2073902A 33

to 6 carbon atoms or an alkylamino group having 1 to 6 carbon atoms; m is 0, 1 or 2; and /7 is 1 or 2;

(II)

10 (H0)^ 10

wherein R' represents a hydrogen atom or an alkyl group; X' represents a hydrogen or halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, 15 an alkylsulfonyl group, an aryloxy group, an acyl group, an acyloxy group or an acylamido 15

group; m' is 0, 1 or 2; and ri is 1 or 2.

10. A photographic material as claimed in Claim 9, wherein said organic base M is trimethylamine or triethylamine.

11. A photographic material as claimed in Claim 9, wherein R is hydrogen, M is sodium or

20 potassium, m is 0 and n is 1. 20

12. A photographic material as claimed in Claim 9, wherein R' is hydrogen, m' is 0 and n'

is 1.

13. A photographic material as claimed in Claim 9, wherein said recurring unit of formula (I) is formed by polymerization of any of Monomers (A) to (E) shown hereinbefore.

25

14. A photographic material as claimed in any one of Claims 9 to 13, wherein the second 25 subbing layer contains a hydrophilic colloid binder in addition to said polymer.

15. A photographic material as claimed in any preceding claim, wherein the second subbing layer includes both a gelatin derivative as defined in any of Claims 1 to 7 and a polymer as defined in any of Claims 9 to 1 3.

30

16. A photographic material as claimed in any preceding claim, wherein said second 30

subbing layer has a thickness of 0.01 to 1.0 micron.

17. A photographic material as claimed in any preceding claim, wherein the first subbing layer contains a copolymer which increases the adhesion of the layer to the film support.

18. A photographic material as claimed in any preceding claim, wherein the first subbing

35 layer contains a hardening agent for that layer. 35

1 9. A photographic material as claimed in any preceding claim, wherein the support is of polyethylene terephthalate.

20. A photographic light-sensitive material as claimed in Claim 1, substantially as hereinbefore described with reference to any of Samples (1 5) to (1 9), (22) to (26), (32) to (37), (41) to

40 (45) or (51) to (59) of Examples 1 to 5. 40

21. A photographic light-sensitive material as claimed in Claim 9, substantially as hereinbefore described with reference to any of Samples (62) to (67), (72) to (77) or (82) to (85) of Examples 6 to 8.

Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Ltd.—1981.

Published at The Patent Office. 25 Southampton Buildings. London, WC2A 1AY, from which copies may be obtained.